Manufacture of dyes



. ethyl Patented July 14, 1942 UNITED STATES PATENT OFFICE 7 mmmscruan orpyns George Holland Ellis, Henry Charles Olpin, and John Wright, Spondon, near Derby, England, assignors to Celanese Corporation of America,

a corporation of Delaware No Drawing, Application December -2o, 19:9,

. Serial No.

This invention relates to the production of new dyes and to the production of textile materials,

andcellulose ester and ether products coloured therewith.

'According to the present invention valuable new azo dyes are prepared by coupling diazotised ylene diamines capable of coupling in para-position to the non-acidylated amino group. Coupling components particularly suitable for purposes of the invention are the mono-acidyl-mphenyl diamines of the general formula wherein B represents hydrogen, halogen, alkyl, or alkoxy (including substituted alkoxy, e. g. p-hydroxyethoxy) Ac represents an acidyl group derived from an aliphatic or aromatic carbexylic acid, particularly a fatty acid containing less than 5 carbon atoms or a benzene carboxylic acid, and R1 represents hydrogen or alkyl (including substituted alkyl e. g. hydroxyethyl or other bydroxyalkyl), and R2 and R3 represent organic substituents for example, alley], aryl, aralkyl, or

cycloalkyl groups (including substituted 'alkyl, aryl, aralkyl or cycloalkyl groups) or where R2 represents an organic substituent and R3 represents hydrogen. If desired, R: and R: may together constitute a chain of methylene groups forming, together with the associated nitrogen atom, a heterocyclic ring, tor example the piperidine ring. Of especial value are the coupling components of this general formula in which R1 represents hydrogen, R: and R: represent alkyl groups, for example, ethyl, methyl, hydroxyor hydroxypropyl, and Ac represents an acidyl group derived from a fatty acid containing less than 5 carbon atoms,

7 for example, the acetyl group or the propio'nyl group. g i It will be appreciated that the dyes are characterised by containing at least two aao groups 7 amino azo compounds with monoacidyI-m-phen 310,176. In Great Britain December '20 Claims; ((11. 8-48) shades may be obtained, particularly navy blue to black shades, which have very good fastness'propertie's. Moreover, many of these shades can readily be discharged, for example, by means of zinc formaldehyde sulphoxylate.

Diazo components suitable for the purposes of the invention are azo-benzenes, azo-a-naphthalenes and benzene-azo-a-naphthalenes' containing one or two diazotisable amino groups in paraand having a residue of a mono-acidyl m-phenylene diamine-as an end component.

. The new dyes can be produced in substance oron a textile material, artificial-straws, foils or the like. Particularly valuable results can be obtained by forming the new dyes on textile materials, straws, foils, or the like made from cellulose acetate or other cellulose ester or ether.

forming the dyes on-these materials dark positions to azo groups. Substituents may be present in addition to the diazotisable amino groups and the azo groups, for examplpe, alkyl groups, acidylamino groups, (e. g. acidylamino groups of the type mentioned above in connec-' tion with the coupling component) alkoxy groups, e. g. methoxy or ethoxygroups, halogen atoms, or nitro groups, the latter two types of substituents more particularly in a nucleus,

which does'not contain a diazotisable amino group. Sulphonic and carboxylic groups are preferably absent from the diazo components tion are diazo oompments of the general-formula x NOFQN==N NH:

wherein X represents hydrogen, alkoxy, hy--v droxy-allnvloxy, alkyl or halogen, Y represents alkoxy, alkyl, halogen or acidylamino, and Z represents hydrogen, nitro or halogen. Such amino-a o compounds can be prepared by coupling diazotised p-nitraniline or the appropriate halogen derivative thereof, or 2:4-dinitraniline, with the appropriately substituted para coupling aniline, e. g. m-toluidine, cresidine, p-xylidine,

2:5-dimethonv anline, 2:5- diethoxy aniline, 'mono-acetyl-m-phenylene diamine, 4-acetylamino-2-amino-toluene, 2-amino-4-acetylamino-anisole, 2 aminoA-scetylamino-l-hydroxyethowbenzene, mono-benzoyl-m-phenylene diamine or 1-amino-3-acetyl-methylamino-benzen e. As coupling components for the production of uid'containing the requisite proportion of diazo the new dyes on cellulose ester or ether or other materials especial mention may be made of the mono-acidyl-m-phenylene diamines of the formulagiven above, wherein B is hydrogen, and particularly those compounds wherein B and R1 are hydrogen, R2 and R3 are alkyl or substituted alkyl groups, and Ac is an acidyl group derived from a fatty acid containing less than 5 carbon atoms, particularly acetic acid or from a benzene carboxylic acid. Examples of such compounds are. 3-acetyl-amino-l-dimethylamino-benzene, 3-acetyl-amino-l-diethylamino-benzene, and 3-acetylamino-l-di(hydroxyethyl) amino-benzene, B-acetylamino 1 (N ethyl-N-hydroxy-ethyl) -amino-benzene, and the corresponding benzoylderivatives.

Coupling components of the above general formulain which B is a substituent, e. g., alkoxy are more particularly of value for the production of dyes in substance. Such coupling components are 3-acetylamino-6-methoxy 1 diethylaminobenzene and 3-acetylamino-6-methyl-l-diethylamino-benzene.

The following table gives some of the diazo components which have.- been found especially suitable for the production of the new dyes on cellulose ester or ether materials. It also gives v the shades obtainable when the diazo compounds in question are diazotised on cellulose acetate materials and coupled with 3-acetylamino-1-diethylamino-benzene Diem component Shade Bright navy blue to 4-nitro-4-amlno-25'-diethoxy-azo-benzene Navy blue. l-nitrobenzene-azo-a-naphthylamine Do. 4-nitro-2 chlorbenzene-am-naphthylamme G r e e n 1 s h n a v y ue. 4-nitro-2chlor-U-amiuo-2-methyl-5'-meth0xy- Navy blue.

2110- M110. blue. 4-nitro-2-chlor-25-dimethoxy-azo-benzene I Do. 4-nitro-4-amino-am-benzene 714.11%.

4-nitro-4amino-2'-methyl-azo-benzene.

terials, it is preferred to incorporate the diazo component in the material and then to' effect diazotisation and couple with the coupling component in a separate bath.

' The diazo components can be applied to cellulose ester or ether materials in the form of aqueous dispersions. Bath methods may be employed, that is to saymethods in which the materials are allowed to absorb the diazo component from an aqueous dispersion of the latter I in which they are immersed. -Again, mechanical impregnation 'methods may be used, the materials being impregnated with a quantity of liqcomponent. To this end padding or printing methodsmay be utilised. The mechanicallyimpregnated material may then be agedor steamed to cause the diazo component to enterythe cellulose ester or ether material. v

If a diazo component having substantive afiin-.

ity for cellulose esters or ethers but substantially no substantive aflinity for cellulose is applied to mixed materials containing both cellulose (e. g. cotton or regenerated cellulose) and a cellulose ester or ether, the latter alone takes up the diazo component, so that on diazotising and coupling with the monoacidyl m-phenylene diamine the cellulose component of the material remains uncoloured. By suitably colouring the cellulose component of such mixed material with dyestuffs resisting the cellulose ester or ether component of the materials solid shades or two colour effects can readil be obtained according to the components and dye selected. The dyestufi for the cellulose portion can be applied before or after the development of the azo dye on the cellulose ester or ether portion. If desired, however, it

may be applied before development and.either together with or separately from the diazo component applied to the cellulose ester or ether portion. If the dyestufi for the cellulose component is diazotisable it can be diazotised and deemployed in accordance with the present invention for the formation of an azo dye on the cellulose ester or ether component of the material'may simultaneously be used to develop the diazotised dyestufi on the cellulose component of the mixed material. It will be appreciated that the mono-acidyl-m-phenylene diamines can be' used to couple with diazotised amino-azocompounds for the production of azo dyes on textile materials generally and whether cellulose ester or ether material is present or not. For example a textile material composed wholly of cotton or regenerated cellulose can be allowed to take up a diazotisable substantive azo dye and the latter'diazotised on the material and developed with a mono-acidyl-m-phenylene diamine in manner similar to that described above in connection with the-colouring of the cellulose component of a textile containing both cellulose and a cellulose ester or ether.

The dyeings produced on cellulose ester or ether materials in accordance with the invention may be subsequently topped with other dyes and particularly with dyestuffs having direct aflinity for the cellulose ester or ether. For example, a navy blue shade produced according to the invention may be topped with an orange dye or with both a red dye and a yellow dye in order to produce a very dark navy or black shade. Such topping colours may, if desired, be applied to the material before the diazotisation of the lose ester or ether materials that'navy blue to black shades of commercially desirable hue can be obtained directly and without recourse to any topping process.

As mentioned abovethe new dyes can also beproduced in substance. In this form they can be employed for colouring cellulose ester or ether materials by direct dyeing methods though, in

general, this methodof colouring such materials is less advantageous than the method of forming the dyes on the fibre as described above. When formed in substance the dyes are of particular value for colouring cellulose ester or ether solutions, especially lacquers and spinning solutions. By shaping and settingsuch i 3, A dis-azo dye of which each aryl nucleus is selected from the group consisting of the benzene nucleus and the naphthalene nucleus, the said dye having as the end component avresidue of a V mono-acidyl-meta-phenylene-diamine capable of coupling in the para position to the non-acidyl- 1 ated amino group, and of which the non-acidylated amino group carries at least. one alkyl group as a substituent.. a

. 4. A dis-am dye of which each aryl nucleus selected from the group consisting of the benzene nucleus and the naphthalene nucleus, the said dye having as the endcomponent a residue of a mono-acidyl-meta-phenylene-diamine of the general formula v BI n ,\'N n, I i

from a carboxylic acid, R1 represents hydrogen or alkyl, and R: and Rs represent alkyl. I 5. An azo dye of the general formula 'where X is selected from the class consistingof hydrogen, alkoxy, hydroxyalkox'y, alkyl and halogen, Y is selected from the class consisting of hydrogen and alkyl, Z is selected from the class consisting of hydrogen, nitro and halogen, Acis an acidyl residue of a carboxylic acid. R1 and R2 are alkyl groups, and B is selected from the class consisting of hydrogen, halogen, alkyl and alkoxy.

6. An azo dye according to claim 5, wherein'Ri a is hydrogen, Ac is acetyl and B is hydrogen.

7. An azo dye of the formula 10. Process for the coloration of textile materials which comprises forming an azo dyethereon by coupling a diazot'ized amino aao compound, said amino azo'compo'und being one in which each aryl nucleus is selected from the 8rd? consisting of the benzene nucleus the naphtha- Flin with a mono-acidyl m phenylene-diamine wherein 13 represents hydrogen, halogen, alkyl or alkoxy, Ac represents an acidyl group derived lene nucleus, with a mono-acidyl-meta-phenylenediamine of the general formula;

where Ac represents an acidyl group derived from a fatty acid containing less than 5 carbon atoms and R: and R3 represent alkyl groups.

11. Process for the coloration of cellulose acetate materials, which comprises incorporating therein an amino-mono-azo compound of which each aryl nucleus is selected from the group consisting of the benzene nucleus and the naphthalene nucleus and thereafter diazotizing and conof the general formula wherein Ac represents an acidyl group derived from a fatty acid containing less than 5 carbon atoms andRa and R: represent alkyl groups.

' 12. Process for the coloration of cellulose acetate materials which comprises incorporating therein an amino-azo compound obtainable by diazotizing a nitro-aniline and coupling. with a para couplingprimary amine of the benzene series, and thereafter diazotizing said amino-azo compound and coupling with a mono-acidyl-mphenylene-diamine' of the general formula wherein Ac represents an acidyl grou derived from a fatty acid containing less than 5 carbon atoms and R: and R3 represent alk'yl groups.

13. Process for the coloration of cellulose acetate materials which comprises incorporating thereinan amino-azo ,compound of the general formula A mic?- wherein X represents hydrogemalkoxy, alkyl or halogen, Y represents alkoxy, alkyl, halogen or acidylamino, and Z represents hydrogen, nitro or halogen, and thereafter diazotizing said amlno-azo compound and coupling it with a monoacidyl-m-phenylene-diamine of the gen-' eral formula wherein Ac represents an acidyl group-derived from a fatty acid containing less than 5 carbon atoms and R2 and R: represent alkyl groups.

l4. Process for the coloratior'rof cellulose acetate materials which comprises incorporating of soap and Turkey red oil.

solutions in the form of filaments, straws, films and the like valuable coloured products can be 'produqed. For example, coloured cellulose acetate filaments can be produced by dry spinning such coloured solutions. The coloured products so obtained by spinning methods can be topped with suitable direct dyeing dyes or mixtures of dyes in order to produce a wide range of deep shades. For this purpose it is particularly advantageous to spin filaments containing a proportion of dye such that the product is of a blue shade- A single product of this kind can, bysuitable choice of topping colour, be caused to yield a very large number of commercially desirable'shades.

The invention is illustrated by the following examples.

Example 1 1 parts of finely milled 10% aqueous paste of 4-nitro-4-amino-2:5'-dimethoxy-azo benzene is dispersed in 3,000 parts of water with the aid 100' parts of cel-. lulose acetate fabric is dyed in this bath at 78 to 80C. for about 2 hours.v The material is then removed from the bath, rinsed and diazo-' tised for 30 minutes at ordinary temperature in a 30:1 bath prepared with parts of concentrated hydrochloric acid and 5 parts of sodium nitrite. The diazotised material is then rinsed and entered into a cold :1 coupling bath con-' taining 2 parts of 3-acetylamino-1-dieth'ylaminobenzene dispersed with 10 parts of Turkey red oil. After working for a short time cold the temperature is raised to 60 C. which is maintained for half an hour. 1 The material is then rinsed and soaped for half an hour at 60 C. in

a solution containing 0.25 grams per litre of soap. A full navy blue shade of excellent fastness properties is thus otbained; it can readily be discharged with soluble zinc formaldehyde nitro-4'-amino-2':5'-dimethoxy-azo benzene a black shade is obtained;

By substituting half the quantity of 4-nitro- 4'-amino-2'-acetylamino-5'-metlioxy-azo benzene for the-4-nitro-2';5'-dimethoxy-azo hen zene and 1' part of 3-.acetylamino-l-diethylamino-benzene or 1 part of 3-acetylamino-1- di(p-h ydroxyethyl) -amingi-benzene for the 2 parts of s-acetylamino-l-diethylamino-benzene specified above. a greenish navy blue shade is obtained.

Example 2 A fabric consisting of cellulose acetate artificial silk and viscose artificial silk in equal proportions by weight is dyed with 5% of its weight of a 10% paste of 4-nitro-4'-amino-2':5'-dimethoxy-azo-benzene and 2.5% of its weight of Diazo Indigo Blue BR from a 30:1 bath, the

former being dispersed in the bath with soap and Turkey red oil. The materialis then rinsed and both dyes diazotised in the manner described in Example 1. After rinsing, the diazotised material is introduced at 50 0. into a 30:1 bath containing, based on the weight of the goods, 3% of 3-acetylamino-l-diethylaminobenzene dispersed with 3 times its weight of Turkey red oil and 0.2% of soda ash. The material is treated in the bath for hour while the temperature is raised to60 C.- Flnally the material is rinsed and soaped in a 1 gram per litre soap solution for A hour at '60 C. A solid navy blue shade is obtained. 4

By increasing the proportion of 4 -nitro-4'- amino-2':5'-dimethoxy-azo-benzene to 10% and substituting 3.5% of Oxydiaminogen OT for the 2.5% of Diazo Indigo Blue BR a solid black shade results. By using other diazotisable dyes for colouring the viscose a wide range of two colour efiects can 'be obtained. Examples of such dyes are Diazo Brilliant Orange-5G, Diazo Fast Red 'ZBL, Dlazo Brilliant Blue BBLA, Biazo Fast Green GL, Diazo Fast Green GRL and Chlorazol Black BH.

Example 3 portions by weight is dyed with 5% of its weight sulphoxylate. By doubling the quantity of 4- of a 10% paste of 4-nitro-4'-amino-2':5'-dimethoxy-azo-benzene. Diazotisation and coupling, using 2% of its weight of 3-acetylamino-ldiethylamino benzene, followed by soaping are then carried out in the mannerdescribed in Example 2. Prior to the last 10 minutes of the soaping 0.2 gram of sodium hydrosulphite are added per litr of the soaping bath toO remove any traces of .colour formed on the viscose.

The cellulose acetate part of the material is thus coloured navy blue leaving the viscose uncoloured.

' Example 4 A suspension of 30.2 parts of 4-nitro-4'-amino- 2':5'-dimethoxy-azo-benzene in 180 parts of glacial acetic acid is slowly added to a solution of nitrosyl sulphuric acid made from 7.2 parts of sodium nitrite and 140 parts of 96% sulphuric acid. The temperature is maintained at 10-15 C. during the addition and for 1 hours thereafter. After adding 2 parts of sulphamic acid the soltuion is run slowly into a well-stirred solution of 20.7 parts of 3-acetylamino-1-diethylaminobenzene in 2500 parts of 10% sodium acetate solution to which has been added 17 parts of concentrated hydrochloric acid. After stirring for a further A hour the product is filtered ofi, washed and dried.

1 part of the above colouring matter is milled with'25'parts of a 10% solution of'cellulose acetate in acetone in which the colouring matter dissolved in part at least. Sufficient cellulose acetate and acetone are then added to form a solution containing 25% of cellulose acetate and .0625% of the colouring matter. This solution is spun into filaments by dry-spinning methods. The filaments are blue in colour and can be overdyed with suitable dischargeable dyes having direct aflinity for cellulose acetate to give a wide range of dischargeable brown, green, grey and navy blue shades.

Having described our invention, what we desire to secure by Letters Patent is:

1. Process for the production of an azo dye which comprises coupling a diazotized amino azo compound, of which each aryl nucleus is selected from the group consisting of the benzene nucleus and the naphthalene nucleus, with 'a mono- I acidyl-meta-phenylene-diamine capable of coupling in ,the para position to the non-acidylated amino group.

2. A dis-azo dye of which each aryl nucleus is selected from the group consisting of the benzene nucleus and the naphthalene nucleus, said dye having, as the end component the residue of a mono-acidyl meta-phenylene-diamine capable of coupling in the para position to the non-acidylated amino group.

4.nitro-4'-amino-2':5'-dimethoxy azo benzene therein, and thereafter diazotizing and coupling with 3-acetylamino-l-diethylamino-benzene.

15. Process for the coloration of cellulose acetate materials which comprises incorporating 4- 5 nitro-4'-amino-2'-acetylamino 5'-methoxy-azobenzene therein, and thereafter diazotizing andcoupling with 3-acetylamino-1-diethylaminobenzene. l

16. Process tor the coloration of cellulose scetate materials which comprises incorporating 4- nitro-4'-amino-2'-acetylamino-5f -methoxy a-zobenzene therein, and thereafter diazotizing and coupling with 3-acetylamino 1 -di(p-hydroxyethyl) -amino-benzene.

17. Textile materials coloured with a. dye

' claimed in claim a.

18. Cellulose acetate materials coloured with a'dye'claimed in claim 4. v

19. Cellulose acetate materials coloured with a dye claimed in claim 5.

. 2o. Cellulose acetate materials coloured yvith a.

lo dye claimed in claim 9.

GEORGE HOLLAND ELLIS. HENRY CHARLES oLPm. JonN WRIGHT. 

